CN109962234A - Monocrystalline positive electrode of concentration gradient and preparation method thereof - Google Patents

Monocrystalline positive electrode of concentration gradient and preparation method thereof Download PDF

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Publication number
CN109962234A
CN109962234A CN201910247492.7A CN201910247492A CN109962234A CN 109962234 A CN109962234 A CN 109962234A CN 201910247492 A CN201910247492 A CN 201910247492A CN 109962234 A CN109962234 A CN 109962234A
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positive electrode
concentration gradient
presoma
concentration
monocrystalline
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CN201910247492.7A
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Chinese (zh)
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江卫军
乔齐齐
许鑫培
施泽涛
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蜂巢能源科技有限公司
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Priority to CN201910247492.7A priority Critical patent/CN109962234A/en
Publication of CN109962234A publication Critical patent/CN109962234A/en

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    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of or comprising active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of or comprising active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses monocrystalline positive electrodes of concentration gradient and preparation method thereof, wherein, preparation method includes: to be placed in reaction kettle by carrier of nickel hydroxide particle, sodium hydroxide solution is added as precipitating reagent simultaneously, ammonium hydroxide is added as complexing agent, and controlling the reactor temperature is 50-60 degrees Celsius, pH value 10-12, atmosphere is nitrogen；Manganese salt solution is pumped into the first feed rate into reaction kettle, cobalt salt solution is pumped into the second feed rate, so that manganese salt and cobalt salt deposit in the hole of nickel hydroxide particle, to synthesize presoma；Calcination process is carried out after presoma is mixed with lithium salts, to obtain the monocrystalline positive electrode of concentration gradient.The preparation method has simple process, the advantages that at low cost, material structure is stablized, the advantages of monocrystalline positive electrode for the concentration gradient being prepared has both concentration gradient material and monocrystal material, can be avoided the Particle Breakage problem of material, while be effectively improved the cycle performance and security performance of material.

Description

Monocrystalline positive electrode of concentration gradient and preparation method thereof
Technical field
The invention belongs to lithium ion battery amount fields, specifically, the present invention relates to the monocrystalline positive electrodes of concentration gradient And preparation method thereof.
Background technique
Lithium ion battery is widely used as a kind of efficient energy storage and conversion equipment.However, positive material Expect that specific capacity is lower, constrains the promotion of lithium ion battery specific energy.In current several positive electrodes, tertiary cathode material It is with the obvious advantage in terms of specific discharge capacity, voltage and structural stability.Currently, tertiary cathode material mainly has second particle and list It is two kinds brilliant.For second particle material relative to monocrystal material, structural stability is poor, and dusting and electrolyte are easy in cyclic process Side reaction is more.Its structural stability can be improved in second particle material by synthesizing concentration gradient, reduces in the electrolytic solution Dissolution improves cycle performance.On the other hand, monocrystalline positive electrode has compacted density height, good cycle, stable structure, production The advantages such as gas is few.However, as the cycle progresses, the Ni on monocrystalline positive electrode surface is easily formed non-electroactive phase NiO, Material capacity is caused to reduce.Therefore, existing monocrystalline positive electrode is further improved at present.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention One purpose is to propose that a kind of preparation method of the monocrystalline positive electrode of concentration gradient, the preparation method have simple process, The advantages that at low cost, material structure is stablized, the monocrystalline positive electrode for the concentration gradient being prepared have both concentration gradient material and It the advantages of monocrystal material, can be avoided the Particle Breakage problem of material, while being effectively improved cycle performance and the safety of material Energy.
According to an aspect of the present invention, the invention proposes the preparation method of the monocrystalline positive electrode of concentration gradient, roots According to the embodiment of the present invention, which includes:
It is placed in reaction kettle by carrier of nickel hydroxide particle, while sodium hydroxide solution is added as precipitating reagent, be added Ammonium hydroxide is as complexing agent, and controlling the reactor temperature is 50-60 degrees Celsius, and pH value 10-12, atmosphere is nitrogen；
Manganese salt solution is pumped into the first feed rate into the reaction kettle, cobalt salt solution is pumped into the second feed rate, So that manganese salt and cobalt salt deposit in the hole of the nickel hydroxide particle, to synthesize presoma；
Calcination process is carried out after the presoma is mixed with lithium salts, to obtain the monocrystalline positive electrode of concentration gradient.
The present invention is used as carrier using loose porous little particle nickel hydroxide, by cobalt salt and manganese salt pass through reaction kettle according to Concentration variation is deposited in nickel hydroxide, passes through the conditions such as control reaction atmosphere, temperature, pH value, charging rate, synthesis concentration ladder The little particle presoma of degree.By presoma and lithium salts by high-temperature roasting, the monocrystalline positive electrode of concentration gradient is obtained.The present invention Then the presoma being distributed by pre-synthesis graded elemental concentrations obtains the gradient anode of monocrystalline through high-temperature roasting with lithium salts again Material.The monocrystalline positive electrode of the concentration gradient of this method synthesis is relative to traditional monocrystalline positive electrode, in Ni constituent content Portion is conducive to the generation of the Ni segregation and non-electroactive phase NiO that inhibit positive electrode surface, while Mn and Co more than outside Element surface is conducive to the structural stability for keeping material more than inside.Therefore, the material that the present invention synthesizes has stable structure The features such as property is higher, cycle performance is more excellent.And the preparation method that the present invention uses has simple process and low cost, material The advantages that stable structure.
In addition, the preparation method of the monocrystalline positive electrode of concentration gradient according to the above embodiment of the present invention can also have Following additional technical characteristic:
In some embodiments of the invention, the partial size of the nickel hydroxide particle is 1-4um, porosity 50%.
In some embodiments of the invention, the reactor temperature is 50-55 degrees Celsius, pH value 11-12.
In some embodiments of the invention, the concentration of the sodium hydroxide solution is 2mol/L, the concentration of the ammonium hydroxide For 0.5mol/L.
In some embodiments of the invention, the manganese salt solution is selected from MnSO4、Mn(NO3)2With Mn (CH3COO)2In At least one aqueous solution.
In some embodiments of the invention, the molar concentration of manganese is 1mol/L in the manganese salt solution.
In some embodiments of the invention, the cobalt salt solution is selected from CoSO4、Co(NO3)2With Co (CH3COO)2In At least one aqueous solution.
In some embodiments of the invention, the molar concentration of cobalt is 1mol/L in the cobalt salt solution.
In some embodiments of the invention, first feed rate is the ascending rate of 1mL/min.
In some embodiments of the invention, second feed rate is the ascending rate of 1mL/min.
In some embodiments of the invention, the lithium salts is LiOH, Li2CO3Or CH3COOLi, preferably LiOH.
In some embodiments of the invention, the mass ratio of the presoma and the lithium salts is 100:46.
In some embodiments of the invention, the presoma is (NixCoyMnz)(OH)2And/or (NixCoyMnz)CO3, Wherein, 1/3≤x≤1,0 < y≤1/3,0 < z≤1/3, x+y+z=1.
In some embodiments of the invention, the monocrystalline positive electrode of the concentration gradient has following composition: LiaNixCoyMnzO2, wherein 1≤a≤1.2,1/3≤x≤1,0 < y≤1/3,0 < z≤1/3, x+y+z=1.
According to the second aspect of the invention, the invention also provides a kind of monocrystalline positive electrodes of concentration gradient, according to this Monocrystalline positive electrode preparation method as described in preceding embodiment of the embodiment of invention, the concentration gradient is prepared.As a result, The positive electrode has both the advantages of concentration gradient material and monocrystal material, can be avoided the Particle Breakage problem of material, has simultaneously Effect improves the cycle performance and security performance of material.
Detailed description of the invention
The SEM of the monocrystalline positive electrode of Fig. 1 concentration gradient according to an embodiment of the present invention schemes.
The line scan element distribution map of the monocrystalline positive electrode of Fig. 2 concentration gradient according to an embodiment of the present invention.
The all charging and discharging curve figures of the head of the monocrystalline positive electrode of Fig. 3 concentration gradient according to an embodiment of the present invention.
The cycle performance figure of the monocrystalline positive electrode of Fig. 4 concentration gradient according to an embodiment of the present invention.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, it is intended to for explaining this Invention, and be not considered as limiting the invention.
According to an aspect of the present invention, the invention proposes the preparation method of the monocrystalline positive electrode of concentration gradient, roots According to the embodiment of the present invention, which includes:
It is placed in reaction kettle by carrier of nickel hydroxide particle, while sodium hydroxide solution is added as precipitating reagent, be added Ammonium hydroxide is as complexing agent, and controlling the reactor temperature is 50-60 degrees Celsius, and pH value 10-12, atmosphere is nitrogen；
Manganese salt solution is pumped into the first feed rate into the reaction kettle, cobalt salt solution is pumped into the second feed rate, So that manganese salt and cobalt salt deposit in the hole of the nickel hydroxide particle, to synthesize presoma；
Calcination process is carried out after the presoma is mixed with lithium salts, to obtain the monocrystalline positive electrode of concentration gradient.
The present invention is used as carrier using loose porous little particle nickel hydroxide, by cobalt salt and manganese salt pass through reaction kettle according to Concentration variation is deposited in nickel hydroxide, passes through the conditions such as control reaction atmosphere, temperature, pH value, charging rate, synthesis concentration ladder The little particle presoma of degree.By presoma and lithium salts by high-temperature roasting, the monocrystalline positive electrode of concentration gradient is obtained.The present invention Then the presoma being distributed by pre-synthesis graded elemental concentrations obtains the gradient anode of monocrystalline through high-temperature roasting with lithium salts again Material.The monocrystalline positive electrode of the concentration gradient of this method synthesis is relative to traditional monocrystalline positive electrode, in Ni constituent content Portion is conducive to the generation of the Ni segregation and non-electroactive phase NiO that inhibit positive electrode surface, while Mn and Co more than outside Element surface is conducive to the structural stability for keeping material more than inside.Therefore, the material that the present invention synthesizes has stable structure The features such as property is higher, cycle performance is more excellent.And the preparation method that the present invention uses has simple process and low cost, material The advantages that stable structure.
In addition, usually concentration gradient material can significantly improve the security performance and cycle life of material.But current concentration ladder The positive electrode of degree is mostly second particle, and Particle Breakage situation can occur over numerous cycles for second particle material, to lead Cause cycle performance, the decline of DSC decomposition temperature of material.And monocrystal material can be obviously improved the problem of Particle Breakage.Therefore, this hair The advantages of monocrystalline positive electrode for the concentration gradient that bright success is prepared has both concentration gradient material and monocrystal material can keep away Exempt from the Particle Breakage problem of material, while being effectively improved the cycle performance and security performance of material.
The preparation method of the monocrystalline positive electrode of the concentration gradient of the above embodiment of the present invention is described below in detail.
According to a particular embodiment of the invention, it firstly, being placed in reaction kettle by carrier of nickel hydroxide particle, is added simultaneously Ammonium hydroxide is added as complexing agent as precipitating reagent in sodium hydroxide solution, and controlling the reactor temperature is that 50-60 is Celsius Degree, pH value 10-12, atmosphere is nitrogen.
According to an embodiment of the invention, the method comprises the steps of firstly, preparing nickel-cobalt-manganese ternary presomas, wherein with nickel hydroxide particle For carrier, it is prepared by Supported Manganese and cobalt.The nickel hydroxide particle used has porous little particle hydroxide to be loose Nickel.Specifically, the nickel hydroxide particle that partial size is 50% for 1-4um, porosity is used.The partial size and porosity are used as a result, Nickel hydroxide advantageously form monocrystal material, be also beneficial to improve material compacted density.
According to a particular embodiment of the invention, the reactor temperature is 50-55 degrees Celsius, pH value 11-12, atmosphere For nitrogen.It is possible thereby to which manganese and cobalt is enabled effectively to be enriched in the hole of nickel hydroxide particle.Tool according to the present invention Body example, the temperature in reaction kettle is unsuitable excessively high or too low, otherwise will affect Mn and Ni metal ion deposition velocity and point The uniformity of cloth；And the tap density of material can be improved in suitable pH value；In addition, atmosphere is nitrogen, Jin Erke in reaction kettle It is oxidized to avoid metal ion.
According to a particular embodiment of the invention, the reactor temperature is preferably 50-55 degrees Celsius, and pH value is preferably 11-12 atmosphere is nitrogen.Presoma is prepared under the preferred reaction conditions, can be further improved tap density, the shape of material Looks integrality.
In addition, ammonium hydroxide is added as complexing agent, as a result, by the way that sodium hydroxide solution is added as precipitating reagent in the step Sodium hydroxide can be reacted with nickel salt, manganese salt, made nickel salt, manganese salt while being precipitated；Ammonium hydroxide can keep PH when precipitating.Specifically The concentration on ground, the sodium hydroxide solution of addition is 2mol/L, this concentration can make nickel salt, and manganese salt settling rate is moderate, protects simultaneously Card precipitating is complete；The concentration of ammonium hydroxide is 0.5mol/L.This ammonia concn can make nickel salt, and manganese salt precipitates generation simultaneously, and generating needs The hydroxide precursor wanted, rather than other kinds of presoma.
According to a particular embodiment of the invention, secondly, being pumped into manganese salt solution into the reaction kettle with the first feed rate, It is pumped into cobalt salt solution with the second feed rate, so that manganese salt and cobalt salt deposit in the hole of the nickel hydroxide particle, so as to Synthesize presoma.The present invention is pumped into rate, and then adjustable hydroxide by control manganese salt solution and cobalt salt solution as a result, To the enriched concentration of surface manganese and cobalt element inside nickel particle, and then obtain the presoma with concentration gradient.
Firstly, according to a particular embodiment of the invention, the manganese salt solution used can be selected from for MnSO4、Mn(NO3)2And Mn (CH3COO)2At least one of aqueous solution.Specific example according to the present invention, the molar concentration of manganese is in the manganese salt solution 1mol/L.Inventors have found that will affect the size distribution of material if the molar concentration of the manganese of manganese salt solution is excessive；And manganese rubs Your concentration is too small, then will affect the pattern of material.
According to a particular embodiment of the invention, the cobalt salt solution is selected from CoSO4、Co(NO3)2With Co (CH3COO)2In At least one aqueous solution.Specific example according to the present invention, the molar concentration of cobalt is 1mol/L in the cobalt salt solution.Invention People's discovery, if the molar concentration of the cobalt of cobalt salt solution is excessive, will affect the size distribution of material；And the molar concentration of cobalt is too small, It then will affect the pattern of material.
In addition, more heavily, according to an embodiment of the invention, inventors have found that by controlling above-mentioned manganese salt solution and cobalt salt Solution is pumped into rate, can make the concentration of the manganese being enriched in the hole of nickel hydroxide particle and cobalt along particle inside extremely Surface is in certain change of gradient, and then be effectivelys prepared to obtain the presoma with certain gradient concentration.
According to a particular embodiment of the invention, wherein manganese salt solution is pumped into reaction kettle with the first feed rate, and cobalt salt is molten Liquid is pumped into reaction kettle with the second feed rate.Specifically, the first feed rate can be the ascending rate of 1mL/min.Second Feed rate can be the ascending rate of 1mL/min.As a result, more inside Ni element in particle in the presoma finally obtained In surface, and Mn and Co element surface is more than inside.And then form the presoma of three element concentration in gradient variation.And Ni element More than outside inside content, it is possible to prevente effectively from the life of the Ni element segregation on positive electrode surface and non-electroactive phase NiO At, while the content surface of Mn and Co element then can effectively keep the structural stability of material more than inside.Therefore, pass through The presoma that can be effectivelyed prepared to obtain element and change in gradient is prepared using the above method, and then can be significantly improved subsequent The structural stability and cycle performance for the positive electrode being prepared.And the preparation method that the present invention uses has technique letter The advantages that list, at low cost, material structure is stablized.
According to a particular embodiment of the invention, the presoma that above-mentioned steps are prepared has following composition: (NixCoyMnz)(OH)2And/or (NixCoyMnz)CO3, wherein 1/3≤x≤1,0 < y≤1/3,0 < z≤1/3, x+y+z=1.By This can satisfy lithium ion battery to the capacity requirement of nickelic positive electrode.
According to a particular embodiment of the invention, finally, above-mentioned be prepared after presoma is mixed with lithium salts is roasted Processing, to obtain the monocrystalline positive electrode of concentration gradient.
According to a particular embodiment of the invention, lithium salts used can be LiOH, Li2CO3Or CH3COOLi.According to the present invention Specific example, lithium salts is preferably LiOH.It is possible thereby to further increase the capacity and cycle performance of positive electrode.
According to a particular embodiment of the invention, the mass ratio of the presoma and the lithium salts is 100:46.
According to a particular embodiment of the invention, it is small that roasting 10 can be carried out after presoma being mixed with lithium salts at 800 DEG C When.And then can remove the water in presoma and lithium hydroxide, so that Li and Ni, Mn, Co is sufficiently mixed, forms the crystalline substance of completion Body structure.
According to a particular embodiment of the invention, the monocrystalline positive electrode of the concentration gradient has following composition: LiaNixCoyMnzO2, wherein 1≤a≤1.2,1/3≤x≤1,0 < y≤1/3,0 < z≤1/3, x+y+z=1, above-mentioned composition meets Capacity requirement of the lithium ion battery to nickelic positive electrode.
The preparation method of the monocrystalline positive electrode of the concentration gradient of the embodiment of the present invention, with the porous nickel hydroxide of little particle For parent, the little particle presoma of concentration gradient is synthesized by the rate of reaction kettle control charging.By presoma and lithium hydroxide Through high-temperature roasting after mixing, the monocrystalline positive electrode of concentration gradient is obtained.The positive electrode that the present invention synthesizes combines gradient material The technical advantage of material and both monocrystal materials, improves material structure stability, it is suppressed that the capacity and voltage attenuation of material, together When synthetic method it is simple and easy.Therefore, the material that the present invention synthesizes can be used for lithium ion battery, improve the property of lithium ion battery Energy.
According to the second aspect of the invention, the invention also provides a kind of monocrystalline positive electrodes of concentration gradient, according to this Monocrystalline positive electrode preparation method as described in preceding embodiment of the embodiment of invention, the concentration gradient is prepared.As a result, The positive electrode has both the advantages of concentration gradient material and monocrystal material, can be avoided the Particle Breakage problem of material, has simultaneously Effect improves the cycle performance and security performance of material.
According to a particular embodiment of the invention, the monocrystalline positive electrode of the concentration gradient has following composition: LiaNixCoyMnzO2, wherein 1≤a≤1.2,1/3≤x≤1,0 < y≤1/3,0 < z≤1/3, x+y+z=1.
Embodiment
Stock: nickel salt is the nickel hydroxide particle that partial size is 1-4um, porosity is 50%；Cobalt salt is CoSO4It is water-soluble Liquid, the molar concentration of cobalt is 1mol/L in cobalt salt solution；Manganese salt is MnSO4, the molar concentration of manganese is 1mol/L in manganese salt solution； Lithium salts is LiOH.
Preparation method: being placed in reaction kettle using above-mentioned nickel hydroxide particle as carrier, controls the reactor temperature and is 50 degrees Celsius, pH value 11, atmosphere is nitrogen, and it is the sodium hydroxide solution of 2mol/L as precipitating reagent that concentration, which is added, is added dense Degree is the ammonium hydroxide of 0.5mol/L as complexing agent；Ascending rate into reaction kettle with 1mL/min is pumped into above-mentioned manganese salt solution, with The ascending rate of 1mL/min is pumped into above-mentioned cobalt salt solution, so that manganese salt and cobalt salt deposit to the hole of the nickel hydroxide particle In, to synthesize presoma；It is roasted 10 hours at 800 DEG C after the presoma of synthesis is mixed with lithium hydroxide, to obtain The monocrystalline positive electrode of concentration gradient.
The presoma group of synthesis becomes Ni0.88Mn0.03Co0.09(OH)2；The group of the positive electrode finally synthesized becomes LiNi0.88Mn0.03Co0.09O2。
Detection and result: respectively to positive electrode carry out electron microscope analysis, the analysis of line scan element, first all analysis by charged and discharged, Capacity retention ratio is analyzed after 1C discharge capacity and 50 weeks circulations.
Fig. 1 is LiNi0.88Mn0.03Co0.09O2SEM figure.It can be seen from the figure that material morphology is monocrystalline, partial size 2- 3um。
Fig. 2 is positive line of material scan element distribution map.It can be seen from the figure that it is more than surface inside Ni element, and Mn With Co element surface more than inside.Accordingly, it is determined that the material that the present invention synthesizes is concentration gradient material.
Fig. 3 is all charging and discharging curve figures of head of positive electrode.It can be seen from the figure that the head week charging of positive electrode 0.1C It is respectively 243.2 and 211.1mAh/g, first charge-discharge efficiency 86.8% with specific discharge capacity.Therefore, the present invention synthesizes Monocrystal material specific discharge capacity is higher.
The positive electrode 1C discharge capacity that Fig. 4 test result display present invention synthesizes is 196.5mAh/g, after 50 weeks recycle, Positive electrode capacity retention ratio is 98.4%.Therefore, the concentration gradient monocrystal material cycle performance that the present invention synthesizes is excellent.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any It can be combined in any suitable manner in a or multiple embodiment or examples.In addition, without conflicting with each other, the technology of this field The feature of different embodiments or examples described in this specification and different embodiments or examples can be combined by personnel And combination.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned Embodiment is changed, modifies, replacement and variant.

Claims (10)

1. a kind of preparation method of the monocrystalline positive electrode of concentration gradient characterized by comprising
It is placed in reaction kettle by carrier of nickel hydroxide particle, while sodium hydroxide solution is added as precipitating reagent, ammonium hydroxide is added As complexing agent, and controlling the reactor temperature is 50-60 degrees Celsius, and pH value 10-12, atmosphere is nitrogen；
Manganese salt solution is pumped into the first feed rate into the reaction kettle, cobalt salt solution is pumped into the second feed rate, so that Manganese salt and cobalt salt deposit in the hole of the nickel hydroxide particle, to synthesize presoma；
Calcination process is carried out after the presoma is mixed with lithium salts, to obtain the monocrystalline positive electrode of concentration gradient.
2. preparation method according to claim 1, which is characterized in that the partial size of the nickel hydroxide particle is 1-4um, hole Gap rate is 50%.
3. preparation method according to claim 1, which is characterized in that the reactor temperature is 50-55 degrees Celsius, pH Value is 11-12；
Optionally, the concentration of the sodium hydroxide solution is 2mol/L, and the concentration of the ammonium hydroxide is 0.5mol/L.
4. preparation method according to claim 1, which is characterized in that the manganese salt solution is selected from MnSO4、Mn(NO3)2 With Mn (CH3COO)2At least one of aqueous solution；
Optionally, the molar concentration of manganese is 1mol/L in the manganese salt solution；
Optionally, the cobalt salt solution is selected from CoSO4、Co(NO3)2With Co (CH3COO)2At least one of aqueous solution；
Optionally, the molar concentration of cobalt is 1mol/L in the cobalt salt solution.
5. the preparation method according to claim 4, which is characterized in that first feed rate is being incremented by for 1mL/min Rate；
Optionally, second feed rate is the ascending rate of 1mL/min.
6. preparation method according to claim 1, which is characterized in that the lithium salts is LiOH, Li2CO3Or CH3COOLi, Preferably LiOH.
7. preparation method according to claim 1, which is characterized in that the mass ratio of the presoma and the lithium salts is 100:46.
8. preparation method according to claim 1, which is characterized in that the presoma is (NixCoyMnz)(OH)2And/or (NixCoyMnz)CO3, wherein 1/3≤x≤1,0 < y≤1/3,0 < z≤1/3, x+y+z=1.
9. preparation method according to claim 1, which is characterized in that under the monocrystalline positive electrode of the concentration gradient has Column composition: LiaNixCoyMnzO2, wherein 1≤a≤1.2,1/3≤x≤1,0 < y≤1/3,0 < z≤1/3, x+y+z=1.
10. a kind of monocrystalline positive electrode of concentration gradient, which is characterized in that the monocrystalline positive electrode of the concentration gradient is by right It is required that the described in any item preparation methods of 1-9 are prepared.
CN201910247492.7A 2019-03-29 2019-03-29 Monocrystalline positive electrode of concentration gradient and preparation method thereof CN109962234A (en)

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